Dyeing, printing, or stencilling of materials made of or containing cellulose derivatives



colouring matters Patented Oct. 18, 1932 nnrran sraras PATENT Fri-E nanny nzanvrus, or mnnon, GEORGE Hermann ELLIS, zronms @CKMA'N, an]: HENRY LES owns, or sronnon, Nnan nanny, ENGLAND, assrenons T0 cnmmnsn COEIPORATION OF AMERICA, .15. CORPORATION OF DELAWARE DYMNG,

PRINTING, 0B STENGILLING OF MATERIALS MADE QB OB CONTAINING CELLULOSE nnmvamvns in Drawing. Application filed April 19,

This application, which is a'continuation in part of U. S. application Serial No. 162,-

938 filed 22nd January 1927, relates to the dyeing, printing, stencilling or otherwise lulose format'e, propionate, or butyrate, or

the products obtained by the treatment of alkalized cellulose with esterii'ying agents (e. g. the product known as immunized cotton), or made of or containing cellulose ethers, such as methyl, ethyl, or benzyl cellulose, or the corresponding condensation products of cellulose and glycols or other polyhydric alcohols, all of which cellulose derivatives are hereinafter referred to as organic substitution derivatives of cellulose.

U. S. application Serial No. 162,938 describes and claims, inter alia, the dyeing or otherwise colouring of the said organic substitution derivatives of cellulose by means of dyestuffs or compounds containing one or more urea or thiourea residues. In theco'urse of further researches it has been found that 85- pecially'us'eful results are obtained by dyeing or otherwise colouring the cellulose acetate or other organic substitution derivatives of cellulose with particular unsulphonated colour ing matters or compounds of this class which contain one urea or thiourea group in which one or more hydrogen atoms of the said group is or are replaced by aryl groups, at least one of which contains one or more nitro groups. The aryl groups may contain further substituents such as halogen, or alkyl, alkyloxy, amino, or acidylamino groups. When the contain diazotizable amino groups they may be diazotized on the materials and developed in the customary manner.

The following table shows the shades given Dlnltrodlaminodiphenylurea fr 1929, Serial No. 356,600, and in Great ZBrltain April 20, 1928.

by some colouring matters which may be used according to the invention.

Colouring matter Shade 2 a-dlnitrophenylurea Yellow 2 4 2 4'-tetranltro-dlphenylurea Yellow phenylenediamine and phosgene G lden yellow The colouring matters-or compounds may be applied in aqueous solution (when sufliciently soluble), or in aqueous suspensions or colloidal solutions or dispersions obtained by grinding (for example in colloid mills), by

dissolving in a solvent and pouring into water containing or not containing protective colloids or dlspersators, by pretreating the colouring matters or compounds with dispersing agents or by other methods. Of the dispersing agents which are suitable for obtaining such dispersions may be mentioned those described in U. S. Patent specifications Nos. 1,618,413, 1,618,414 and 1,694,413, and British Patents Nos. 273,819 and 273,820; viz. bodies of oily or fatty characteristics, namely higher c'tatty acids or sulphonated or other derivatives thereof containing salt-forming groups, such as sulphoricinoleic acid or other sul honated fatty acids or salts of such acids or 'odies', for instance their alkali or ammonium salts, used alone or in conjunction with auxiliary solvents as described in U. S. Patent specification No. 1,690,481 and British Patent No. 269,960; carbocyclic compounds containing in their structure one or more forming groups or salts of such compounds; sulpho-aromatic fatty acids or salts thereof and soluble resin soaps orsodium or other soluble salts of resin acids.

Mixed goods containing for example, in adsalt or the cellulose type of artificial silk or other fibres or threads, may be dyed or otherwise coloured with or without employment of other dyestuffs or -componentsaccording to thecharacter of the threads or fibres used "in association, such other dyestuffs or'.compo-' nents being applied if desired either before or after the application of the colouring matvention but is not to be regarded as limiting it in any way.

Example 1 To dye a yellow shade on 10 kilos of cellulose acetate yai'n in hank form, finely ground 2. -dinitro-phenylurea are well stirred or ground with 1 litre of sodium sulphoricinoleate the mixture is heated under an open steam pipe, and then diluted with boiling water, and further boiled. The liquor is then passed through a filter cloth into a dyeba-th containing 300 litres of cold soft water. 10 kilos of the material are introduced and dyeing is carried out as usual, the temperature being raised in 4 hour to 7580 C. andmaintained at this level as necessary to exhaust. The hanks are 'now lifted, rinsed, and dried, or otherwise treated as requisite.

By replacing the cellulose acetate yarn in this example by mate the latter is likewise dyed in yellow shades.

What we claim and desire to secure by Let ters Patent is 1. Process for dyeing materials comprising organic substitution derivatives of cellulose which comprises applying thereto unsulphonated colouring matters of the general formula 1 R1 Bl \N-CX-N/ Ra Rc where X represents oxygen or sulphur and I R R R and R represent-hydrogen, or

aryl residues but at least one is anitroaryl residue. a

2. Process for dyeing materials comprising organic substitution derivatives of cellulose which comprises applying thereto diazotizable unsulphonated colouring matters of the general formula where X represents oxygen or sulphur and R R R and R represent hydrogen, or aryl but at least one is a nitroaryl residue, and diazotizing and developing with an azo coupling component.

3. Process for dyeing materials comprising cellulose acetate which comprises applying 100 grams of.

yarn made of cellulose forthereto unsulphona-ted colouring matters of the general formula where X represents oxygen or sulphur and R R R and R, represent hydrogen, or aryl residues but at least one is a nitroaryl residue. k

4. Process for dyeing materials comprising cellulose acetate which comprises applying thereto diazotizable unsulphonated colouring matters. of the general formula where X represents oxygen or sulphur and R R R and R. represent hydrogen, or aryl residues but at least one is a nitroaryl residue, and diazotizing and developing with an azo coupling component. i

5. Process for dyeing materials comprising cellulose acetate which comprises applying thereto in aqueous colloidal dispersion unsulphonated colouring matters of the general formula where X represents oxygen or sulphur and R R R and R, represent hydrogen, or aryl residues but at least one is a nitroaryl residue.

6. Materials comprising organic substitution derivatives of cellulose dyed with unsulphonated colouring matters of the general formula R1 Ra \t-cx R|/ Ra where X represents oxygen or sulphur and R R R and R represent hydrogen, or aryl residues but at least one is a nitroaryl residue.

7. Materials comprising cellulose acetate dyed with unsulphonated colouring matters of the general formula where X represents oxygen or sulphur and R R R and R. represent hydrogen, or aryl residues at least one is a nitroaryl residue.

8. Process for dyeing materials comprising organic substitution derivatives of cellulose which comprises applying thereto unmesses sulphonated colouring matters consisting of compounds of the formula:

mansion.

where X represents oxygen or sulphur, substituted in at least one of the groups by at least one nitroaryl residue.

9. Process for dyeing materials comprisin cellulose acetate which comprises apply= b o ring thereto unsulphonated colouring matters consisting of compounds of the formula:

NH QXNIL. where represents oxygen or sulphur, substituted in at least one of the Nlhl groups by at least one nitrouryl residue.

10. Process-for dyeing materials compris ing organic substitution derivatives of cellulose which comprises applying thereto diazotizableunsulphonated colouring matters con= sisting of compounds oi the formula:

where X represents oxygen or sulphur, substituted in at least one of the NH groups by at least one nitroaryl residue and diazotiz- I ing and developing with an azo coupling component.

12-. Process for dyeing materials comprising organic substitution derivatives of cellulose which comprises applying thereto unsulphonated colouring matters consisting 0 compounds of the formula:

' NILEELNH where X represents oxygen or sulphur, substituted in at least one of the Mi -groups by at least one nitrophenyl residue."

13. Process for dyeing materials compris ing cellulose acetate which comprises applying thereto unsulphonated colouring matters consisting of compounds of the formula:

NH .CX.NH

where. X represents oxygen or sulphur, substituted in at least one of the EH groups by at least one nitrophenyl residue.

14. Process for dyeing materials comprising organic substitution derivatives of cellulose which comprises ap-plying thereto diazo= for dyeing materials compris tiaable unsulphonated colouring matters consistmg ot compounds of the formula:

where X represents oxygen or sulphur, substituted in at least one oi the NH groups by at least one nitro'phenyl residue and diazotiming anddeveloping with an arc coupling component.

15. Process for dyein materials comprising cellulose acetate which comprises applying thereto diazotizable unsulphonated colouring matters consisting of compounds of the formulafi unions-n2,

where X represents oxygen or sulphur, substituted in at least one or the NH groups by at least one nitrophenyl residue and diaaotizing and developing with an azo coupling component.

16. Materials comprising organic substitu tion derivatives of cellulose dyed with un-x sulphonated colouring matters consisting of compounds oi; the formula:

where X is oxygen or sulphur, substituted in at least one of the NH groups by at least one nitroaryl residue:

17. Materials comprising cellulose acetate dyed with unsulphonated colouring matters consisting of compounds of the formula:

NH .OX.li H

where X is oxygen or sulphur, substituted in at least one oi the NR groups by at least one nitroaryl residue.

18. Materials comprising organic substitu tion derivatives of cellulose dyed with unsul= phonatedcolouring matters consisting of compounds of the formula:

NI-LOEQNEL. where X is oxygen or sulphur, substituted in i at least one of the NH groups by at least one nitrophenyl residue.

19. Materials comprising cellulose acetate dyed with unsulphonated colouring matters consisting of compounds of the formula:

where X is oxygen or sulphur, substituted in at least one of the NIL groups by at least one nitrophenyl residue.

In testimony whereof we have hereunto subscribed our names.

HENRY DREYFUS. GEORGE HGLLAND ELLIS. TOBIAS OCKMZAN. HENRY CHARLES OLPIN. 

